JP2006008475A - Method for manufacturing photocatalyst titanium oxide - Google Patents
Method for manufacturing photocatalyst titanium oxide Download PDFInfo
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- JP2006008475A JP2006008475A JP2004190896A JP2004190896A JP2006008475A JP 2006008475 A JP2006008475 A JP 2006008475A JP 2004190896 A JP2004190896 A JP 2004190896A JP 2004190896 A JP2004190896 A JP 2004190896A JP 2006008475 A JP2006008475 A JP 2006008475A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 6
- 239000011941 photocatalyst Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 12
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical group O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 11
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 4
- 230000001699 photocatalysis Effects 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000010936 titanium Substances 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 14
- 238000010304 firing Methods 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- -1 titanium hydride Chemical compound 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 2
- OVSGBKZKXUMMHS-VGKOASNMSA-L (z)-4-oxopent-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O OVSGBKZKXUMMHS-VGKOASNMSA-L 0.000 description 1
- XAVMMNWPOYCFPU-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanolate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].OCCN(CCO)CC[O-].OCCN(CCO)CC[O-] XAVMMNWPOYCFPU-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- VMRRWRGQFHFGGP-UHFFFAOYSA-N C(C)[Ti]OCCCCCC Chemical compound C(C)[Ti]OCCCCCC VMRRWRGQFHFGGP-UHFFFAOYSA-N 0.000 description 1
- LLQPHQFNMLZJMP-UHFFFAOYSA-N Fentrazamide Chemical compound N1=NN(C=2C(=CC=CC=2)Cl)C(=O)N1C(=O)N(CC)C1CCCCC1 LLQPHQFNMLZJMP-UHFFFAOYSA-N 0.000 description 1
- CDQFODAJQFUTJR-UHFFFAOYSA-M [NH4+].[O-]C(=O)C(=O)O[Ti] Chemical compound [NH4+].[O-]C(=O)C(=O)O[Ti] CDQFODAJQFUTJR-UHFFFAOYSA-M 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 1
- 229940094800 barium oxalate Drugs 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- IAOQICOCWPKKMH-UHFFFAOYSA-N dithieno[3,2-a:3',2'-d]thiophene Chemical compound C1=CSC2=C1C(C=CS1)=C1S2 IAOQICOCWPKKMH-UHFFFAOYSA-N 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HQASLXJEKYYFNY-UHFFFAOYSA-N selenium(2-);titanium(4+) Chemical compound [Ti+4].[Se-2].[Se-2] HQASLXJEKYYFNY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、光触媒酸化チタンの製造方法に関し、詳しくは光触媒酸化チタン前駆体を焼成して光触媒酸化チタンを製造する方法に関する。 The present invention relates to a method for producing photocatalytic titanium oxide, and more particularly to a method for producing photocatalytic titanium oxide by firing a photocatalytic titanium oxide precursor.
光触媒酸化チタンは、酸化チタンを主成分とし、光触媒活性を示す物質であり、例えば鏡などの表面にコートして親水化し、水滴の付着を防止するためなどに用いられている〔特許文献１：特開平９−５７９１２号公報〕。かかる光触媒酸化チタンの製造方法としては、光触媒酸化チタン前駆体を焼成する方法が知られている〔特許文献２：特開２００１−３０２２４１号公報〕。 The photocatalytic titanium oxide is a substance mainly composed of titanium oxide and exhibiting photocatalytic activity. For example, the photocatalytic titanium oxide is used to coat a surface of a mirror or the like to make it hydrophilic and prevent adhesion of water droplets [Patent Document 1: JP-A-9-57912]. As a method for producing such photocatalytic titanium oxide, a method of firing a photocatalytic titanium oxide precursor is known [Patent Document 2: JP 2001-302241 A].
しかし、従来の製造方法で光触媒酸化チタンを製造すると、得られる酸化チタンの光触媒活性がばらつき易いという問題があることが分かった。 However, it has been found that when photocatalytic titanium oxide is produced by a conventional production method, the photocatalytic activity of the resulting titanium oxide tends to vary.
そこで本発明者は、光触媒活性のばらつきを招くことなく、高い活性の光触媒酸化チタンを製造し得る方法を開発するべく鋭意検討した結果、光触媒酸化チタン前駆体を水分と接触させることなく焼成した後、１００℃〜６００℃の温度にて水分と接触させることにより、高活性の光触媒酸化チタンを安定的に製造し得ることを見出し、本発明に至った。 Therefore, the present inventor has eagerly studied to develop a method capable of producing a highly active photocatalytic titanium oxide without causing a variation in photocatalytic activity. The present inventors have found that a highly active photocatalytic titanium oxide can be stably produced by bringing it into contact with moisture at a temperature of 100 ° C. to 600 ° C., leading to the present invention.
すなわち本発明は、光触媒酸化チタン前駆体を水分と接触させることなく焼成したのち、１００℃〜６００℃にて水分と接触させることを特徴とする光触媒酸化チタンの製造方法を提供するものである。 That is, this invention provides the manufacturing method of the photocatalytic titanium oxide characterized by making a photocatalyst titanium oxide precursor contact with a water | moisture content at 100 to 600 degreeC after baking without making it contact with a water | moisture content.
本発明の製造方法によれば、活性のばらつきを招くことなく、安定して高活性の光触媒酸化チタンを製造することができる。 According to the production method of the present invention, highly active photocatalytic titanium oxide can be produced stably without causing variations in activity.
本発明の製造方法で使用される光触媒酸化チタン前駆体は、焼成により光触媒活性を示す酸化チタンに導かれる化合物であって、例えば窒化チタン、ホウ化チタン、臭化チタン、炭化チタン、水素化チタン、ヨウ化チタン、水酸化チタン、酸化チタン、セレン化チタン、硫化チタン、テルル化チタン、硫酸チタン〔Ｔｉ（ＳＯ4）2・ｍＨ2Ｏ、０≦ｍ≦２０〕、オキシ硫酸チタン〔ＴｉＯＳＯ4・ｎＨ2Ｏ、０≦ｎ≦２０〕、三塩化チタン〔ＴｉＣｌ3〕、四塩化チタン〔ＴｉＣｌ4〕、オキシ塩化チタン〔ＴｉＯＣｌ2〕、四臭化チタン〔ＴｉＢｒ4〕、シュウ酸チタンアンモニウム、シュウ酸チタンバリウム、オルトチタン酸、メタチタン酸などのチタン含有無機化合物、
テトラメトキシチタン、テトラエトキシチタン、テトラ−ｎ−プロポキシチタン、テトライソプロポキシチタン、テトラ−ｎ−ブトキシチタン、テトライソブトキシチタン、テトラ−ｓｅｃ−ブトキシチタン、テトラ−ｔ−ブトキシチタン、テトラキス−２−エチルヘキシロキシチタン、テトラステアリロキシチタンのようなテトラアルコキシチタン化合物、
ジイソプロポキシビス（アセチルアセトナト）チタン、ジイソプロポキシビス（トリエタノールアミナト）チタン、ジ−ｎ−ブトキシビス（トリエタノールアミナト）チタン、ジ（２−エチルヘキシロキシ）ビス（２−エチル−１，３−ヘキサンジオラト）チタン、イソプロポキシ（２−エチルヘキサンジオラト）チタン、テトラアセチルアセトネートチタン、ヒドロキシビス（ラクタト）チタンのようなチタンキレート化合物などのようなチタン含有有機化合物を主成分とするものが挙げられる。また、上記したチタン含有無機化合物およびチタン含有有機化合物は、一部が加水分解されていてもよいし、一部が結晶性酸化チタンに結晶化していてもよい。中でも、水酸化チタン、オルトチタン酸、メタチタン酸、酸化チタン、窒化チタンを主成分が好ましい。
The photocatalytic titanium oxide precursor used in the production method of the present invention is a compound that is led to titanium oxide that exhibits photocatalytic activity by firing. For example, titanium nitride, titanium boride, titanium bromide, titanium carbide, titanium hydride , Titanium iodide, titanium hydroxide, titanium oxide, titanium selenide, titanium sulfide, titanium telluride, titanium sulfate [Ti (SO 4 ) 2 .mH 2 O, 0 ≦ m ≦ 20], titanium oxysulfate [TiOSO 4 NH 2 O, 0 ≦ n ≦ 20], titanium trichloride [TiCl 3 ], titanium tetrachloride [TiCl 4 ], titanium oxychloride [TiOCl 2 ], titanium tetrabromide [TiBr 4 ], titanium ammonium oxalate, Titanium-containing inorganic compounds such as barium oxalate, orthotitanic acid, metatitanic acid,
Tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetra-sec-butoxy titanium, tetra-t-butoxy titanium, tetrakis-2- Tetraalkoxytitanium compounds such as ethylhexyloxytitanium, tetrastearyloxytitanium,
Diisopropoxybis (acetylacetonato) titanium, diisopropoxybis (triethanolaminato) titanium, di-n-butoxybis (triethanolaminato) titanium, di (2-ethylhexyloxy) bis (2-ethyl-) Mainly titanium-containing organic compounds such as titanium chelate compounds such as 1,3-hexanediolato) titanium, isopropoxy (2-ethylhexanediolato) titanium, tetraacetylacetonate titanium, hydroxybis (lactato) titanium The thing made into a component is mentioned. Moreover, a part of the above-described titanium-containing inorganic compound and titanium-containing organic compound may be hydrolyzed, or a part thereof may be crystallized into crystalline titanium oxide. Of these, titanium hydroxide, orthotitanic acid, metatitanic acid, titanium oxide, and titanium nitride are preferred as main components.
前駆体の焼成は、水分と接触させることなく行われ、具体的には水蒸気濃度２ｖｏｌ％未満、好ましくは１ｖｏｌ％以下、さらに好ましくは水蒸気濃度が０ｖｏｌ％で実質的に水蒸気を含まない乾燥状態の雰囲気中で行われる。焼成する際の雰囲気ガスは、大気であってもよいし、アルゴンなどの希ガス、窒素ガスなどの不活性ガスであってもよい。焼成温度は通常１００℃、好ましくは１２０℃以上、さらに好ましくは１５０℃以上、通常は８００℃以下、好ましくは６００℃以下であり、焼成に要する時間は通常０．１時間〜３０時間程度である。 The precursor is calcined without contact with moisture, specifically, a water vapor concentration of less than 2 vol%, preferably 1 vol% or less, more preferably a water vapor concentration of 0 vol% and in a dry state substantially free of water vapor. Performed in an atmosphere. The atmosphere gas at the time of firing may be air, or may be a rare gas such as argon, or an inert gas such as nitrogen gas. The firing temperature is usually 100 ° C., preferably 120 ° C. or more, more preferably 150 ° C. or more, usually 800 ° C. or less, preferably 600 ° C. or less. The time required for firing is usually about 0.1 to 30 hours. .
焼成により、光触媒酸化チタン前駆体は通常、アナターゼ型の酸化チタンに遷移する。焼成により得られた酸化チタンは、冷却することなく、そのまま直ちに本発明で規定する温度にて水分と接触させてよいし、一旦冷却した後、再び加熱して、本発明で規定する温度にて水分と接触させてもよい。 By firing, the photocatalytic titanium oxide precursor usually transitions to anatase-type titanium oxide. The titanium oxide obtained by firing may be immediately contacted with moisture at a temperature specified in the present invention without cooling, or once cooled and then heated again at a temperature specified in the present invention. It may be brought into contact with moisture.
水分と接触させるには、通常、雰囲気中の水蒸気濃度を２ｖｏｌ％〜８０ｖｏｌｏ％、好ましくは６０ｖｏｌ％以下として、この濃度範囲の水蒸気と接触させる。水分と接触させる際の雰囲気ガスは大気であってもよいし、アルゴンなどの希ガス、窒素ガスなどの不活性ガスであってもよい。水蒸気濃度を上記範囲とするには、例えば炉内に水蒸気（スチーム）を雰囲気ガスと共に吹き込み、置換すればよい。水分と接触させる時間は通常０．１時間〜１時間程度である。 In order to contact with moisture, the water vapor concentration in the atmosphere is usually set to 2 vol% to 80 vol%, preferably 60 vol% or less, and the water vapor is brought into contact with this concentration range. The atmosphere gas when contacting with moisture may be air, or may be a rare gas such as argon, or an inert gas such as nitrogen gas. In order to set the water vapor concentration within the above range, for example, water vapor (steam) may be blown into the furnace together with the atmospheric gas and replaced. The time of contact with moisture is usually about 0.1 hour to 1 hour.
水分との接触は、冷却しながら行われることが好ましい。冷却しながら水分と接触させる場合、冷却前後の温度差は通常３０℃以上、好ましくは５０℃以上であり、通常は２００℃以下である。 The contact with moisture is preferably performed while cooling. When contacting with moisture while cooling, the temperature difference before and after cooling is usually 30 ° C. or more, preferably 50 ° C. or more, and usually 200 ° C. or less.
水分と接触させたのち、更に冷却して、目的の光触媒酸化チタンを得る。本発明の製造方法により得られた光触媒酸化チタンは、ばらつきなく高い光触媒活性を示す。 After contacting with moisture, it is further cooled to obtain the desired photocatalytic titanium oxide. The photocatalytic titanium oxide obtained by the production method of the present invention exhibits high photocatalytic activity without variation.
以下、実施例によって本発明をより詳細に説明するが、本発明は、かかる実施例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
なお、各実施例で得た光触媒酸化チタンの光触媒活性は、以下の方法で評価した。
(1)光触媒活性
直径８ｃｍ、高さ１０ｃｍ、容量約０．５Ｌ（５００ｃｍ3）の密閉式ガラス製反応容器内に、直径５ｃｍのガラス製シャーレを載置し、その上に、光触媒酸化チタン０．３ｇを載せ、反応容器内を酸素／窒素比が１：４（体積比）の混合ガスで満たし、更にアセトアルデヒド１３．４μモルを封入し、反応容器の外側から可視光を照射する。可視光は、５００Ｗキセノンランプ〔ウシオ電機社製、「ランプＵＸＬ−５００ＳＸ」〕を取付けた光源装置〔ウシオ電機社製、「オプティカルモジュレックスＳＸ−Ｕ１５００ＸＱ」〕から、波長４３０ｎｍ以下の紫外線を遮蔽する紫外線カットフィルター〔旭テクノガラス社製、「Ｙ−４５」〕を通して照射する。可視光を照射している間、反応容器内の二酸化炭素の濃度を光音響マルチガスモニタ〔ＩＮＮＯＶＡ社製、「１２１３型」〕により測定して、光触媒酸化チタン１ｇあたりの二酸化炭素生成速度を求める。二酸化炭素生成速度が高いほど、光触媒活性が高い。
(2)ＢＥＴ比表面積
窒素吸着法により測定した。
In addition, the photocatalytic activity of the photocatalytic titanium oxide obtained in each Example was evaluated by the following method.
(1) A glass petri dish having a diameter of 5 cm is placed in a closed glass reaction vessel having a photocatalytic activity diameter of 8 cm, a height of 10 cm, and a capacity of about 0.5 L (500 cm 3 ). .3 g is placed, the inside of the reaction vessel is filled with a mixed gas having an oxygen / nitrogen ratio of 1: 4 (volume ratio), 13.4 μmol of acetaldehyde is further sealed, and visible light is irradiated from the outside of the reaction vessel. Visible light shields UV light with a wavelength of 430 nm or less from a light source device (USHIO INC., “Optical Modlex SX-U1500XQ”) equipped with a 500 W xenon lamp (USHIO INC., “LAMP UXL-500SX”). Irradiate through an ultraviolet cut filter [Asahi Techno Glass, "Y-45"]. While irradiating visible light, the carbon dioxide concentration in the reaction vessel is measured by a photoacoustic multi-gas monitor (“INNOVA, Model 1213”) to determine the carbon dioxide production rate per gram of photocatalytic titanium oxide. The higher the carbon dioxide production rate, the higher the photocatalytic activity.
(2) The BET specific surface area was measured by a nitrogen adsorption method.
参考例１〔光触媒酸化チタン前駆体の製造〕
オキシ硫酸チタン〔添川理化学社製〕９０ｇを純水３６０ｇに溶解させて水溶液とし、氷冷下に撹拌しながら２５％アンモニア水〔和光純薬工業社製、試薬１級〕１０４ｇを５ｍＬ／分の添加速度で加えて、オキシ硫酸チタンを加水分解させて、スラリーを得た。このスラリーを濾過して固形分を得、温水で洗浄し、１００℃で乾燥して、水酸化チタンの粉末を得た。
Reference Example 1 [Production of photocatalytic titanium oxide precursor]
90 g of titanium oxysulfate (manufactured by Soekawa Richemical Co., Ltd.) was dissolved in 360 g of pure water to obtain an aqueous solution, and 104 g of 25% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1) 104 g was stirred at 5 mL / min. It was added at an addition rate to hydrolyze titanium oxysulfate to obtain a slurry. This slurry was filtered to obtain a solid, washed with warm water, and dried at 100 ° C. to obtain a titanium hydroxide powder.
上記で得た水酸化チタン粉末を炉内で２００℃／時間の昇温速度で３４０℃まで昇温し、同温度で１時間保持して焼成した。焼成は水蒸気濃度０％の乾燥大気中で行った。その後、同じ雰囲気下に２００℃／時間の冷却速度で８０℃まで冷却して、粉末状の酸化チタンを得た。 The titanium hydroxide powder obtained above was heated to 340 ° C. at a temperature increase rate of 200 ° C./hour in a furnace, and held at the same temperature for 1 hour for firing. Firing was performed in a dry atmosphere with a water vapor concentration of 0%. Then, it cooled to 80 degreeC by the cooling rate of 200 degreeC / hour under the same atmosphere, and obtained the powdery titanium oxide.
実施例１
参考例１で得た酸化チタンを炉内で水蒸気濃度０％の大気中、再び２００℃／時間の昇温速度で３４０℃まで昇温し、同温度を１時間保持した後、同じ雰囲気下で２００℃／時間の冷却速度で冷却を開始した。３００℃まで冷却した時点で、炉内に水蒸気濃度３．３ｖｏｌ％の大気を導入して炉内を置換し、更に２００℃まで冷却した時点で、再び水蒸気濃度０ｖｏｌ％の大気を炉内に導入して置換した。５０℃まで冷却した後、酸化チタン粉末を取り出し、二酸化炭素生成速度を求めたところ、１ｇあたり６．６μモル／時間であった。また、ＢＥＴ比表面積は９１ｍ2／ｇであった。
Example 1
In the furnace, the titanium oxide obtained in Reference Example 1 was heated to 340 ° C. again at a rate of temperature increase of 200 ° C./hour in the atmosphere with a water vapor concentration of 0%. Cooling was started at a cooling rate of 200 ° C./hour. At the time of cooling to 300 ° C., the atmosphere with a water vapor concentration of 3.3 vol% was introduced into the furnace to replace the inside of the furnace, and when it was further cooled to 200 ° C., the air with a water vapor concentration of 0 vol% was again introduced into the furnace. And replaced. After cooling to 50 ° C., the titanium oxide powder was taken out and the carbon dioxide production rate was determined to be 6.6 μmol / hour per gram. The BET specific surface area was 91 m 2 / g.
実施例２
参考例１で得た酸化チタン粉末を炉内で水蒸気濃度０％の大気中、２００℃／時間の昇温速度で３５０℃まで昇温し、同温度を１時間保持した後、２００℃／時間の冷却速度で５０℃まで冷却した。冷却開始時に炉内に水蒸気濃度１１ｖｏｌ％の大気を導入して置換し、更に２７５℃まで冷却した時点で、再び水蒸気濃度０ｖｏｌ％の大気を炉内に導入した。冷却後の酸化チタン粉末の二酸化炭素生成速度は１ｇあたり７．６μモル／時間であった。また、ＢＥＴ比表面積は６０ｍ2／ｇであった。
Example 2
The titanium oxide powder obtained in Reference Example 1 was heated to 350 ° C. at a rate of temperature increase of 200 ° C./hour in an oven with a water vapor concentration of 0% in the furnace, held at that temperature for 1 hour, and then 200 ° C./hour. It cooled to 50 degreeC with the cooling rate of. At the start of cooling, an atmosphere with a water vapor concentration of 11 vol% was introduced into the furnace for replacement, and when it was further cooled to 275 ° C., an air with a water vapor concentration of 0 vol% was again introduced into the furnace. The carbon dioxide production rate of the titanium oxide powder after cooling was 7.6 μmol / hour per gram. The BET specific surface area was 60 m 2 / g.
比較例１
参考例１で得た酸化チタンは光触媒活性を示し、二酸化炭素生成速度は１ｇあたり５．６μモル／時間であった。
Comparative Example 1
The titanium oxide obtained in Reference Example 1 showed photocatalytic activity, and the carbon dioxide production rate was 5.6 μmol / hour per gram.
比較例２
参考例１で得た水酸化チタン粉末を炉内で２００℃／時間の昇温速度で３４０℃まで昇温し、同温度で１時間保持して焼成した。焼成は水蒸気濃度３．３％の大気中で行った。その後、同じ雰囲気下に２００℃／時間の冷却速度で８０℃まで冷却して、粉末状の酸化チタンを得た。得られた媒酸化チタンの二酸化炭素生成速度は、光触媒活性を示し、二酸化炭素生成速度は１ｇあたり５．１μモル／時間であった。
Comparative Example 2
The titanium hydroxide powder obtained in Reference Example 1 was heated in a furnace to 340 ° C. at a temperature increase rate of 200 ° C./hour, and held at that temperature for 1 hour for firing. Firing was performed in an atmosphere having a water vapor concentration of 3.3%. Then, it cooled to 80 degreeC by the cooling rate of 200 degreeC / hour under the same atmosphere, and obtained the powdery titanium oxide. The carbon dioxide production rate of the obtained titanium oxide showed photocatalytic activity, and the carbon dioxide production rate was 5.1 μmol / hour per gram.
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| JP2007260534A (en) * | 2006-03-28 | 2007-10-11 | Sumitomo Chemical Co Ltd | Method for preparing titanium oxide photocatalyst |
| US7641890B2 (en) | 2006-03-20 | 2010-01-05 | Fujifilm Corporation | Inorganic fine particle and method for producing the same using microchannel |
| JP2011016062A (en) * | 2009-07-08 | 2011-01-27 | Fukuoka Univ | Method of producing photocatalyst of nonmetallic-element-doped titanium oxide |
| CN114797943A (en) * | 2022-06-08 | 2022-07-29 | 重庆工商大学 | Oxygen-rich vacancy and nitrogen-doped TiO 2 Preparation method of catalyst, product and application thereof |
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| JPH06192140A (en) * | 1992-09-15 | 1994-07-12 | Inst Fr Petrole | Method of isomerization of olefin |
| JPH08510472A (en) * | 1994-03-01 | 1996-11-05 | アンスティテュ フランセ デュ ペトロール | Olefin isomerization method |
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| JPH06192140A (en) * | 1992-09-15 | 1994-07-12 | Inst Fr Petrole | Method of isomerization of olefin |
| JPH08510472A (en) * | 1994-03-01 | 1996-11-05 | アンスティテュ フランセ デュ ペトロール | Olefin isomerization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7641890B2 (en) | 2006-03-20 | 2010-01-05 | Fujifilm Corporation | Inorganic fine particle and method for producing the same using microchannel |
| JP2007260534A (en) * | 2006-03-28 | 2007-10-11 | Sumitomo Chemical Co Ltd | Method for preparing titanium oxide photocatalyst |
| JP2011016062A (en) * | 2009-07-08 | 2011-01-27 | Fukuoka Univ | Method of producing photocatalyst of nonmetallic-element-doped titanium oxide |
| CN114797943A (en) * | 2022-06-08 | 2022-07-29 | 重庆工商大学 | Oxygen-rich vacancy and nitrogen-doped TiO 2 Preparation method of catalyst, product and application thereof |
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